TY - JOUR
T1 - Electrochemical behavior of the Cp*(dithiolato)Co(III) complex [(η5-Cp*)Co(1,2-S2C2 B10H10-S,S′)] and its derivatives
T2 - The effect of the ligand on half-sandwich cobalt(III) complexes
AU - Kim, Bo Young
AU - Lee, Chongmok
AU - Chung, Seung Won
AU - Lee, Young Joo
AU - Pak, Jae Youn
AU - Ko, Jaejung
AU - Kang, Sang Ook
N1 - Funding Information:
We thank Prof. Sukbok Chang at the Korean Advanced Institute of Science and Technology (KAIST) for helpful discussions. Financial support from the Korean Science & Engineering Foundation (R01-2000-00050) and the Korea Research Foundation (2001-041-D00119) is gratefully acknowledged.
PY - 2003/12/15
Y1 - 2003/12/15
N2 - Reaction of the 16-electron dithiolatocobalt, [(η5- Cp*)Co(CabS,S′)] (1) (CabS,S′=1, 2-S2C2B10H10-S,S′), with a ligand L (L=CNtBu, PMe3, PEt3, PHPh2) affords the 18-electron complexes [(η5- Cp*)Co(CabS,S′)(L)] (2) in high yield. The structures of 2 in solution were probed by NMR spectroscopy, and the solid-state structure of the diphenylphosphine derivative was established by single-crystal X-ray diffraction. Cyclic voltammetry of 1 shows that the complex undergoes a quasi-reversible one-electron oxidation and reversible reduction. The voltammetry of the corresponding 18-electron complex 2 was investigated rather extensively in terms of coordination and redox chemistry, in which the influence of the enhanced steric interaction between the bulky Cp* and incoming ligand could be observed. Cyclic voltammograms of alkylidiene or acetylene adducts of dithiolatocobalt complex 1, [(η5-Cp*)Co{η 3-(S,S′, C′)-SC2B10 H10S(C′R2)}] [C′R2=CHSiMe 3 (3a), HC=CPh (3b), (COOMe)C=C(COOMe) (3c)], are also included.
AB - Reaction of the 16-electron dithiolatocobalt, [(η5- Cp*)Co(CabS,S′)] (1) (CabS,S′=1, 2-S2C2B10H10-S,S′), with a ligand L (L=CNtBu, PMe3, PEt3, PHPh2) affords the 18-electron complexes [(η5- Cp*)Co(CabS,S′)(L)] (2) in high yield. The structures of 2 in solution were probed by NMR spectroscopy, and the solid-state structure of the diphenylphosphine derivative was established by single-crystal X-ray diffraction. Cyclic voltammetry of 1 shows that the complex undergoes a quasi-reversible one-electron oxidation and reversible reduction. The voltammetry of the corresponding 18-electron complex 2 was investigated rather extensively in terms of coordination and redox chemistry, in which the influence of the enhanced steric interaction between the bulky Cp* and incoming ligand could be observed. Cyclic voltammograms of alkylidiene or acetylene adducts of dithiolatocobalt complex 1, [(η5-Cp*)Co{η 3-(S,S′, C′)-SC2B10 H10S(C′R2)}] [C′R2=CHSiMe 3 (3a), HC=CPh (3b), (COOMe)C=C(COOMe) (3c)], are also included.
KW - 18-Electron dithiolate
KW - Cyclic voltammetry
KW - Dithiolatocobalt
KW - Redox process
UR - http://www.scopus.com/inward/record.url?scp=0242487681&partnerID=8YFLogxK
U2 - 10.1016/j.jorganchem.2003.09.019
DO - 10.1016/j.jorganchem.2003.09.019
M3 - Article
AN - SCOPUS:0242487681
SN - 0022-328X
VL - 688
SP - 236
EP - 245
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 1-2
ER -